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EP2423185B1 - Nouvelles dispersions resorcinol-formaldéhyde-latex, fibres avec adhérence améliorée, leur procédé de préparation et leur application. - Google Patents

Nouvelles dispersions resorcinol-formaldéhyde-latex, fibres avec adhérence améliorée, leur procédé de préparation et leur application. Download PDF

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Publication number
EP2423185B1
EP2423185B1 EP11177348.7A EP11177348A EP2423185B1 EP 2423185 B1 EP2423185 B1 EP 2423185B1 EP 11177348 A EP11177348 A EP 11177348A EP 2423185 B1 EP2423185 B1 EP 2423185B1
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EP
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Prior art keywords
formaldehyde
resorcinol
latex
moiety
aqueous
Prior art date
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Not-in-force
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EP11177348.7A
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German (de)
English (en)
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EP2423185A1 (fr
Inventor
Wilhelm Laufer
Anke Blaul
Armin Eckert
Andrea Fruth
Ana Maria Cano Sierra
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Lanxess Deutschland GmbH
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Rhein Chemie Rheinau GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • C08G8/22—Resorcinol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

Definitions

  • the present invention relates to novel aqueous resorcinol-formaldehyde latex dispersions, adhesion-enhanced fibers, processes for their preparation and their use for improving the adhesion in the tire.
  • Carbodiimides are widely used to treat tire cords, see US-A-3867181 and DE-A-1770495 and US3661623 ,
  • Resorcinol-formaldehyde-latex dispersions have prevailed especially in the tire sector, as they improve the adhesion of the plastic fabric (cord) to the rubber.
  • blocked isocyanates are added to the RFL dip with caprolactam (see US A 20080300347 ). These in turn have the disadvantage that in the further process toxic monomeric isocyanates are eliminated.
  • EP-A 2159241 the use of microencapsulated dimeric diphenylmethane-4,4'-diisocyanate and diphenylmethane-2,4-diisocyanate (MDI) to improve the adhesion-promoting properties known.
  • MDI diphenylmethane-2,4-diisocyanate
  • the substances described here have the disadvantages that they are expensive and commercially unavailable and can also cleave toxic monomeric diisocyanates.
  • the object of the present invention was therefore to provide aqueous resorcinol-formaldehyde-latex dispersions which can be used to improve adhesion and do not have the disadvantages of the prior art.
  • carbodiimides Due to their production, the carbodiimides are frequently produced in mixtures of monomeric, oligomeric and / or polymeric carbodiimides. These mixtures are included in the subject matter of the invention.
  • lactams particularly preferably caprolactam, phenols, novolaks, resorcinol, oxime, polyethylene glycols and / or epoxides.
  • the compounds of the formulas (I) to (V) are commercially available, for example from Rhein Chemie Rheinau GmbH, or can be prepared by the processes familiar to the person skilled in the art, as described, for example, in US Pat DE-A-11 30 594 or US 2,840,589 or by the condensation of diisocyanates with elimination of carbon dioxide at elevated temperatures, for example at 40 ° C to 200 ° C, in the presence of catalysts.
  • catalysts for example, strong bases or phosphorus compounds have been proven.
  • phospholene oxides, phospholidines or phospholine oxides and the corresponding sulfides are used.
  • tertiary amines basic metal compounds, carboxylic acid metal salts and non-basic organometallic compounds can be used.
  • All diisocyanates are suitable for the preparation of the carbodiimides and / or polycarbodiimides used, preference being given in the context of the present invention to using carbodiimides and / or polycarbodiimides which are based on C 1 -C 4 -alkyl-substituted aromatic isocyanates, such as, for example, Toluene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 2,6-diisopropylphenyl isocyanate, 2,4,6-triisopropylphenyl 1,3-diisocyanate, 2,4,6-triethylphenyl-1,3-diisocyan
  • carbodiimides and / or polycarbodiimides are based on 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate or a mixture of 2,4-tolylene diisocyanate and tolylene 2,6-diisocyanate.
  • the solid carbodiimides used particularly preferably have a particle size of ⁇ 50 ⁇ m.
  • the aqueous resorcinol-formaldehyde-latex dispersions according to the invention may contain further additives, such as e.g. rheological aids (anti-settling agents), e.g. Borchi®Gel ALA (OMG Borchers GmbH) or Kelzan® S available from Monsanto or Tragacanth available from R.T. Vanderbilt, stabilizers, emulsifiers, wetting and / or dispersing agents, e.g. Tamol® NN 9104 from BASF AG or Aerosol® OT45 from Cytec Surface Specialties GmbH, Dispersogen® HR from Clariant International Ltd.
  • rheological aids e.g. Borchi®Gel ALA (OMG Borchers GmbH) or Kelzan® S available from Monsanto or Tragacanth available from R.T. Vanderbilt
  • stabilizers emulsifiers
  • wetting and / or dispersing agents e.g. Tamol® NN
  • the resorcinol-formaldehyde-latex dispersions according to the invention are at least one dispersion of the individual components resorcinol and formaldehyde and / or formaldehyde together with a precondensate of resorcinol and formaldehyde (eg Rhenosin® T from Rhein Chemie Rheinau GmbH and Penacolite ® 50 available from Indspec Chemical Corp.) and one or more of the latex dispersion mentioned below.
  • a precondensate of resorcinol and formaldehyde eg Rhenosin® T from Rhein Chemie Rheinau GmbH and Penacolite ® 50 available from Indspec Chemical Corp.
  • XSBR latex carboxylated styrene-butadiene copolymers
  • HS-SBR latex styrene-butadiene copolymers
  • NBR latex nitrile-butadiene copolymers
  • CR latex CR latex (polychloroprene)
  • PSBR latex pyridine-styrene Butadiene-vinylpyridine copolymer latexes, styrene-butadiene-vinylpyridine copolymer latices (eg, Pliocord VP 106, US Pat. available from Eliochem) are preferred.
  • These are commercial substances which are e.g. are available from Polymer Latex GmbH or Eliokem.
  • the resorcinol-formaldehyde-latex dispersion is preferably obtained by stirring in a basic aqueous mixture of resorcinol and formaldehyde or preferably a basic aqueous mixture of formaldehyde and the precondensate of resorcinol and formaldehyde in a basic aqueous latex mixture.
  • the ratio of resorcinol to formaldehyde is preferably 1: 1 to 2.5: 1.
  • the ratio of latex, based on its solids content, to the condensate of resorcinol and formaldehyde is preferably from 10: 1 to 4: 1, more preferably 6: 1.
  • aqueous basic solutions used are preferably aqueous sodium hydroxide and / or ammonium hydroxide solutions. In this case, pH values of 10 to 11 are preferred.
  • the carbodiimides are preferably used in amounts of 0.5 to 10%, more preferably 5-8%, based on the solids content in the resorcinol-formaldehyde latex dispersion.
  • the present invention furthermore relates to a process for the preparation of the resorcinol-formaldehyde-latex dispersions according to the invention, according to which at least one of the compounds of the formula (I) to (V), in bulk or in the form of an aqueous dispersion, is converted into the resorcinol-formaldehyde-latex Dispersion is stirred
  • the aqueous dispersion of the compounds of the formula (I) to (V) are formed preferably by stirring the compounds of the formula (I) to (V), optionally with the addition of further additives, such as. B. rheological aids (anti-settling agent), such as. B. Borchi®Gel ALA (OMG Borchers GmbH) or Kelzan® S, available from the company Monsanto, or Tragacanth, available from R.T. Vanderbilt, stabilizers, emulsifiers, wetting and / or dispersing agents, e.g. Tamol® NN 9104 from BASF AG or Aerosol® OT45 from Cytec Surface Specialties GmbH, Dispersogen® HR from Clariant International Ltd. in water.
  • B. rheological aids anti-settling agent
  • B. Borchi®Gel ALA OMG Borchers GmbH
  • Kelzan® S available from the company Monsanto, or Tragacanth, available from R.T. Vanderbilt
  • the proportions of carbodiimides in the abovementioned aqueous dispersion are preferably 1-80%, more preferably 40-60%.
  • the present invention also relates to adhesive formulations comprising at least one inventive aqueous resorcinol-formaldehyde-latex dispersion and additionally an activating agent.
  • Activation agents in the sense of the invention are e.g. Epoxides such as Glycidyl ether GE 500 from Raschig, Bisphenol A Epoxynovolac from Editya Birla Chemical etc.
  • the at least one activating agent according to the invention is preferably stirred into the resorcinol-formaldehyde-latex dispersion, wherein a different metering sequence is not precluded.
  • the present invention further provides processes for improving the adhesion of reinforcing fibers to crosslinked rubber or elastomers, after which the reinforcing fibers (fibers, cord) are introduced into the adhesive formulation according to the invention and then dried or the reinforcing fibers (fibers, cord) are treated in one or more steps with one and / or more of the components of the adhesive formulation of the invention.
  • the fiber in the latter treatment in several steps with first one and / or several components of the adhesive formulation according to the invention, the fiber can be dried in the meantime.
  • the crosslinked rubber or elastomers are preferably (SBR-styrene-butadiene rubber, (BR) -butadiene rubber, (NR-) natural rubber, (IR-) synthetic natural rubber, polyurethane elastomers or mixtures thereof.
  • both preactivated (pretreated) and non-preactivated reinforcing fibers can be used.
  • the preactivated (pretreated) reinforcing fibers are e.g. polyester- or aramid-based fibers which have been treated with a size during their manufacture (spinning).
  • Commercially available products are e.g. at the company KoSa under KoSa Type 793 and KoSa Type 748.
  • the sizes contain epoxides in many cases.
  • the non-pretreated reinforcing fibers are e.g. polyester or aramid based fibers.
  • Commercially available products are e.g. KoSa Type 792.
  • Also included in this invention is a process for improving the adhesion of reinforcing fibers to crosslinked rubber or elastomers, after which preactivated (pretreated) reinforcing fibers are incorporated into the aqueous resorcinol-formaldehyde-latex dispersion of the invention and then dried.
  • fibers in addition to fibers, also means yarns, cords, as well as reinforcing fabrics, based on e.g. Polyester or aramid, such as u.a. Polyethylene terephthalate-based fibers.
  • the present invention further provides adhesion-improved fibers obtainable by contacting the activating agent-pretreated fibers with at least one aqueous resorcinol-formaldehyde latex dispersion according to the invention or by contacting a non-pretreated fiber with at least one adhesive formulation according to the invention, and then drying (fixing) at temperatures of 180 - 260 ° C.
  • the present invention furthermore relates to the use of the resorcinol-formaldehyde-latex dispersion according to the invention optionally in the presence of activating agents for improving the adhesion between reinforcing fibers and elastomers in tires, drive belts, conveyor belts and / or hoses.
  • Table 1 summarizes the quantities used to prepare an aqueous dispersion: ⁇ b> Table 1: ⁇ / b> material
  • Example 1 Ex. 2 TDI carbodiimide 100 Addolink® CBM 100 Aerosol® OT 75 2.4 2.4 water 91 91 Kelzan® S, 3% in water 9 9
  • Table 2 presents the compositions of adhesive formulations for the treatment of preactivated polyester fibers: ⁇ b> Table 2: ⁇ / b> material
  • Example 3 erf
  • Example 4 VV
  • the pre-drying of the treated fibers was carried out at about 135 ° C for about 60 s, the fixation at 230 ° C for 120 s.
  • Vulcanization and adhesion testing were performed according to ASTM D4393.
  • the test elastomer mixture used was Dunlop SP 5320, available from Dunlop, and an activated PET-Gam.
  • the adhesion promoters according to the invention have significant ecological and operational advantages over the compounds known in the prior art.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (10)

  1. Dispersion aqueuse de résorcine-formaldéhyde-latex, contenant au moins un carbodiimide à base de composés de formule (I)

            R'-(-N=C=N-R-)m-R"     (I)

    dans laquelle
    m correspond à un nombre entier de 1 à 500,
    R = alkylène en C1-C18, cycloalkylène en C5-C18, arylène et/ou aralkylène en C7-C12,
    R' = R-NCO, R-NHCONHR1, R-NHCONR1R2, R-NHCOOR3 ou R-NHCO-R5, et R" = -NCO, -NHCONHR1, -NHCONR1R2, -NHCO-R5 ou -NHCOOR3,
    R1 et R2 dans R' étant indépendamment l'un de l'autre identiques ou différents, et représentant un radical alkyle en C1-C6, cycloalkyle en C6-C10 ou aralkyle en C7-C12, et R3 ayant une des significations de R1 ou représentant un radical polyester ou polyamide ou -(CH2)1-(O-(CH2)k-O)g-R4, -C6H4(OH) ou -C6H3(OH)-((CH2)h-C6H4(OH))y,
    et R5 = époxyde, phénol, oxime, résorcine, polyéthylène glycol et/ou lactame, de préférence caprolactame,
    avec 1 = 1 à 3, k = 1 à 3, g = 0 à 12, h = 1 à 2 et y = 1 à 50,
    et
    R4 = H ou alkyle en C1-C4.
  2. Dispersion aqueuse de résorcine-formaldéhyde-latex selon la revendication 1, caractérisée en ce que le carbodiimide correspond à des composés de formule
    Figure imgb0016
     avec R5 = époxyde, phénol, oxime, résorcine, polyéthylène glycol et/ou lactame, de préférence caprolactame,
    Figure imgb0017
     et/ou
    Figure imgb0018
     avec R = alkylène en C1-C18, cycloalkylène en C5-C18, arylène et/ou aralkylène en C7-C12, et les j dans la molécule étant identiques ou différents, et signifiant 1 à 5, et avec p = 0 à 500,
    Figure imgb0019
     avec x = 1 à 500, et/ou
    Figure imgb0020
    avec n = 1 à 20 ;
    et R3 = radical alkyle en C1-C6, cycloalkyle en C6-C10 ou aralkyle en C7-C12, un radical polyester ou polyamide ou -(CH2)1-(O-(CH2)k-O)g-R4,
    avec 1 = 1 à 3, k = 1 à 3, g = 0 à 12, et
    R4 = H ou alkyle en C1-C4.
  3. Dispersion aqueuse de résorcine-formaldéhyde-latex selon la revendication 1 ou 2, caractérisée en ce que la dispersion de résorcine-formaldéhyde-latex est une dispersion des composants individuels résorcine et formaldéhyde et/ou formaldéhyde conjointement avec un précondensat de résorcine et de formaldéhyde et une ou plusieurs dispersions de latex, choisies dans le groupe constitué par : les copolymères de styrène-butadiène carboxylés (latex XSBR), les copolymères de nitrile-butadiène (latex NBR), le polychloroprène (latex CR), les copolymères de pyridine-styrène-butadiène (latex PSBR) et/ou les copolymères d'acrylate pur et/ou de styrène-acrylate (latex d'acrylate) et/ou les latex de copolymères de styrène-butadiène-vinylpyridine.
  4. Procédé de fabrication de dispersions aqueuses de résorcine-formaldéhyde-latex selon une ou plusieurs des revendications 1 à 3, caractérisé en ce qu'au moins un carbodiimide selon une ou plusieurs des revendications 1 à 3 est incorporé dans la dispersion de résorcine-formaldéhyde-latex.
  5. Formulation d'agent adhésif, contenant une dispersion aqueuse de résorcine-formaldéhyde-latex selon une ou plusieurs des revendications 1 à 3 et en outre au moins un agent d'activation.
  6. Formulation d'agent adhésif selon la revendication 5, caractérisée en ce que l'agent d'activation est au moins un époxyde.
  7. Procédé d'amélioration de l'adhésion de fibres de renforcement avec un caoutchouc réticulé et/ou des élastomères, caractérisé en ce que
    - les fibres sont introduites dans une formulation d'agent adhésif selon la revendication 5 ou 6, puis séchées, ou
    - les fibres sont traitées en une ou plusieurs étapes avec un et/ou plusieurs des constituants de la formulation d'agent adhésif selon la revendication 5 ou 6.
  8. Procédé d'amélioration de l'adhésion de fibres de renforcement avec des caoutchoucs réticulés ou des élastomères, caractérisé en ce que les fibres préactivées sont introduites dans une dispersion aqueuse de résorcine-formaldéhyde-latex selon une ou plusieurs des revendications 1 à 3, puis séchées.
  9. Fibres à adhésion améliorée, pouvant être obtenues par mise en contact des fibres prétraitées avec un agent d'activation avec au moins une dispersion aqueuse de résorcine-formaldéhyde-latex selon une ou plusieurs des revendications 1 à 3 ou par mise en contact d'une fibre non prétraitée avec au moins une formulation d'agent adhésif selon la revendication 5 ou 6, puis séchage (fixation) à des températures de 180 à 260 °C.
  10. Utilisation des dispersions aqueuses de résorcine-formaldéhyde-latex selon une ou plusieurs des revendications 1 à 3, éventuellement en présence d'agents d'activation, pour l'amélioration de l'adhésion entre des fibres de renforcement et des élastomères dans des pneus, des courroies d'entraînement, des bandes de transport et/ou des tuyaux.
EP11177348.7A 2010-08-30 2011-08-12 Nouvelles dispersions resorcinol-formaldéhyde-latex, fibres avec adhérence améliorée, leur procédé de préparation et leur application. Not-in-force EP2423185B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11177348.7A EP2423185B1 (fr) 2010-08-30 2011-08-12 Nouvelles dispersions resorcinol-formaldéhyde-latex, fibres avec adhérence améliorée, leur procédé de préparation et leur application.

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Application Number Priority Date Filing Date Title
EP10174548 2010-08-30
EP10189268 2010-10-28
EP10192089 2010-11-22
EP11158814 2011-03-18
EP11177348.7A EP2423185B1 (fr) 2010-08-30 2011-08-12 Nouvelles dispersions resorcinol-formaldéhyde-latex, fibres avec adhérence améliorée, leur procédé de préparation et leur application.

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EP2423185A1 EP2423185A1 (fr) 2012-02-29
EP2423185B1 true EP2423185B1 (fr) 2017-03-01

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US (1) US8481619B2 (fr)
EP (1) EP2423185B1 (fr)
JP (1) JP5859773B2 (fr)
KR (1) KR101884019B1 (fr)
CN (1) CN102432932B (fr)
BR (1) BRPI1104031A2 (fr)
CA (1) CA2750986A1 (fr)
MX (1) MX2011008990A (fr)
RU (1) RU2576270C2 (fr)
TW (1) TWI519509B (fr)

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JP7710317B2 (ja) * 2020-06-03 2025-07-18 バンドー化学株式会社 接着剤組成物、接着構造体及びベルト
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CA2750986A1 (fr) 2012-02-29
US20120071595A1 (en) 2012-03-22
RU2011135870A (ru) 2013-03-27
TW201215589A (en) 2012-04-16
JP2012046750A (ja) 2012-03-08
RU2576270C2 (ru) 2016-02-27
JP5859773B2 (ja) 2016-02-16
MX2011008990A (es) 2012-03-15
KR20120021233A (ko) 2012-03-08
BRPI1104031A2 (pt) 2015-03-24
KR101884019B1 (ko) 2018-07-31
CN102432932A (zh) 2012-05-02
TWI519509B (zh) 2016-02-01
CN102432932B (zh) 2016-03-16
EP2423185A1 (fr) 2012-02-29
US8481619B2 (en) 2013-07-09

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